可描述硅橡胶弹性的理论模型

硅橡胶是一类应用广泛的弹性体材料.然而由于其复杂的三维网络结构,难以实现硅橡胶的理性设计.本研究尝试从单分子弹性入手来建立从硅橡胶微观力学性质到宏观性能之间的关联.首先,通过基于原子力显微镜的单分子力谱实验测量了甲基乙烯基硅橡胶中2个主成分(硅氧烷链和碳-碳链)的单链弹性(包含熵弹性和焓弹性).随后,利用量子力学计算得出上述2种分子链的理论单链弹性.硅氧烷链和碳-碳链的实验曲线均能与理论曲线很好地重合,表明已成功获取了这2种分子链在准无扰环境中的基准弹性.然后,2个主成分的基准弹性同时被整合到传统的橡胶统计学模型中.最终,通过参数可调的新橡胶弹性模型(称作TCQMG模型)描述了3种不同硅橡胶在整个形变范围内的力学性能.此外,借助TCQMG模型模拟了多个交联网络参数对于硅橡胶力学性能的影响,且模拟结果符合实验结果.该模型不仅有助于理解硅橡胶的复杂交联网络结构,还能够为新型硅橡胶的理性设计提供指导.考虑到硅橡胶与其他弹性体在交联网络结构上的相似之处,TCQMG模型有望用于描述这些弹性体的宏观力学性能.     

电解质溶液的分子热力学模型研究进展

"本文从经典溶液理论及半经验模型、近代统计力学理论和分子模拟三大方面阐述了近年来国内外电解质溶液热力学的研究进展。指出电解质溶液的研究已逐渐从经典的溶液理论和半经验模型转向用统计力学理论进行研究, 从电解质的原始模型转向非原始模型。从分子和离子的微观参数出发建立高水平的热力学理论模型, 以预测电解质溶液体系的宏观热力学性质, 是发展的必然趋势。     

高吸水性树脂研究进展

介绍了高吸水性树脂的结构、性能及其表征,结合经典理论与最新研究从热力学和动力学角度阐述其吸水机理,着重分析合成条件,组份和方法对高吸水性树脂性能的影响机制,简略地介绍了高吸水性树脂三十年来的发展及广阔的应用领域,并预测其研究与开发前景     

连锁聚合反应的动态Monte Carlo模拟及其浓度效应

用动态Monte Carlo方法和键长涨落模型相结合分别对自由基聚合、离子聚合动力学过程进行了计算机模拟, 在三维空间中统计了转化率、聚合度、分子量的数量和重量分布, 并将模拟结果和理论预测进行了对比分析, 同时得到不同浓度下均方回转半径与平均链长的标度关系, 说明三维空间中标度指数与浓度的相关性. 还初步考察了扩散对反应体系分子量的影响. 说明动态Monte Carlo方法用于研究连锁聚合反应动力学过程是有效的, 而且能够同时得到经典的聚合反应Monte Carlo模拟方法所难以得到的链构象、分子扩散等空间相关的信息.     

胶原-磺化羧甲基壳聚糖/硅橡胶皮肤再生材料的制备及其对小型猪烫伤创面全层皮肤缺损的修复研究

制备了一种胶原-磺化羧甲基壳聚糖/硅橡胶皮肤再生材料,并以小型猪为模型,考察了其对烫伤全层皮肤缺损的修复性能.首先合成了磺化羧甲基壳聚糖,并对其结构进行了表征.制备了胶原-磺化羧甲基壳聚糖多孔支架,采用扫描电子显微镜(SEM)研究了磺化羧甲基壳聚糖含量对支架微结构的影响.随着磺化羧甲基壳聚糖含量的增大,胶原-磺化羧甲基壳聚糖支架从纤维结构向片状结构转化,且支架的孔径相对变大.采用体外成纤维细胞培养实验证明胶原-磺化羧甲基壳聚糖支架无明显细胞毒性.进一步将胶原-磺化羧甲基壳聚糖支架与硅橡胶膜复合,构建具有双层结构的皮肤再生材料.以小型猪为模型,评价了其对深度烫伤创面的修复性能.大体观察和组织学分析结果显示,胶原-磺化羧甲基壳聚糖/硅橡胶皮肤再生材料具有更快的血管化性能,且经该材料处理的创面能有效支持薄自体皮片的移植成活,实现深度烫伤创面的全层修复.     

质子交换膜燃料电池及电池组模型分析

本文对现有质子交换膜燃料电池以及电池组模型进行比较分析,认为数学模型的建立,可以增加对燃料电池及电池组内部的传递现象和反应机理的认识,同时可以预测电池以及电池组的性能,并且对优化电池结构参数具有指导意义.模型分析包括了现阶段质子交换膜燃料电池单电池模型和电池组模型的基本类别,它们是单电池CFD数值模拟模型、单电池以及电池组性能模拟模型、燃料电池组气体分配模型、系统模型和非稳态模型.比较了几种模型的建模方式及不同模型的应用范围和各自的优缺点.     

碳酸钙与碳化硅对室温硫化硅橡胶的补强作用

在有关硅橡胶补强的研究中,人们已经对ＳｉＯ２ 等补强性填料对硅橡胶的补强作用进行了深入的研究,但对非补强填料对室温硫化硅橡胶的补强作用则相对涉及较少．作者研究了ＣａＣＯ３ 和ＳｉＣ 两类非补强性填料以及填料的粒径与分布对室温硫化硅橡胶拉伸强度、断裂伸长率和耐温性能等的影响,发现合适粒径的非补强性填料对室温硫化硅橡胶有较好的补强效果,且在填料粒径及分布匹配时有最好的补强效果,选用ＳｉＣ时还可以有效提高室温硫化硅橡胶的热稳定性．     

高吸水性枝脂研究进展

介绍了高吸水性树脂的结构,性能及其表征,结合经典理论与最新研究从热力学和动力学角度阐述其吸水机理,着重分析合成条件,组份和方法对高吸水性树脂性能的影响机制,简略地介绍了高吸水性树脂三十年来的发展及广阔的应用领域,并预测其研究与开发前景。     

生物医用抗菌性硅橡胶材料的研究进展

硅橡胶具有对人体组织无毒、生物相容性好等特点，因而广泛用于医疗领域。通常硅橡胶医用材料都需要和人体的内部组织接触，细菌容易通过各种途径入侵，引发感染，因此需要提高硅橡胶材料的抗菌性能。通过对材料进行表面以及本体改性能够提高有机硅橡胶的抗菌性，有关抗菌性硅橡胶材料的研究也是材料学家和医学家非常关注的一个问题。本文通过总结...     

基于回归分析模型与随机过程模型的硅橡胶泡沫应力松弛预测对比

本文针对硅橡胶泡沫的应力松弛实验数据,基于二阶Prony级数,采用非线性回归分析方法(曲线拟合法)、基于Wiener过程的贝叶斯方法、基于Gamma过程的贝叶斯方法进行参数估计从而分别建立预测模型,通过对比三种建模方法的预测值与实验值的偏差,比较了三种建模方法的效果。结果发现,采用曲线拟合的方法进行参数估计,其预测偏差要大于基于Wiener、Gamma随机过程的贝叶斯方法,表明由于考虑了性能退化过程存在的不可避免的随机性,随机过程模型可以更好地预测硅橡胶泡沫的应力松弛趋势,同时由于应力松弛过程是单调增加的,基于非负的Gamma过程的随机过程模型的预测偏差要小于基于Wiener过程的模型。本文工作可为基于高分子材料性能退化数据的退化预测模型的建模提供一种较好的参数估计方法,有助于提高预测结果的准确性。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.